Experimental boron isotope fractionation between tourmaline and fluid: confirmation from in situ analyses by secondary ion mass spectrometry and from Rayleigh fractionation modelling

Tourmaline synthesised in an experiment with low boron excess was analysed in situ by secondary ion mass spectrometry. It revealed significant B isotope zonation with ¹¹B/¹⁰B ratios increasing in the growth direction of the crystals. Trend, magnitude and absolute values strongly support results from high-B-excess isotope fractionation experiments. Furthermore, the closed system B-isotopic evolution of the experimental fluid was modelled by Rayleigh fractionation. The model results are in excellent agreement with the measured B-isotope composition of the run-product fluid. Consequently, low-element-excess experiments are proposed as an ideal approach to determine fluid-solid isotope fractionation factors for systems that are characterised by Rayleigh fractionation.     

Phyllocladane in brown coal from Handlová, Slovakia: Isolation and structural characterization

Aliphatic diterpenes were isolated from brown coal from Handlová, Slovakia, using microwave assisted extraction of mechanically activated coal powder. The parameters of the extraction procedure were optimized to get the target compounds in high yield. The total extract was separated using adsorption chromatography. GC–MS revealed tetracyclic and tricyclic diterpanes in the aliphatic fraction; they were identified as 16α(H)-phyllocladane (83%), isopimarane (11%), 18-norisopimarane (4%), abietane (2%) and fichtelite (<0.1%). It was found that more than 2 g of the most abundant diterpane, 16α(H)-phyllocladane could be extracted from 1 kg of Handlová coal. Because of the scarcity of relevant analytical data, 16α(H)-phyllocladane was thoroughly characterized by spectroscopic and chromatographic methods. A complete set of ¹H and ¹³C NMR data is given including their comparison with published values and ab initio calculations. EI mass and IR spectra of 16α(H)-phyllocladane are shown and discussed. Kováts retention indices measured on two common GC stationary phases are also given.     

Rapid injection of particles and gas into non-fluidized granular material, and some volcanological implications

In diatremes and other volcanic vents, steep bodies of volcaniclastic material having differing properties (particle size distribution, proportion of lithic fragments, etc.) from those of the surrounding vent-filling volcaniclastic material are often found. It has been proposed that cylindrical or cone-shaped bodies result from the passage of “debris jets” generated after phreatomagmatic explosions or other discrete subterranean bursts. To learn more about such phenomena, we model experimentally the injection of gas-particulate dispersions through other particles. Analogue materials (glass beads or sand) and a finite amount of compressed air are used in the laboratory. The gas is made available by rapidly opening a valve—therefore the injection of gas and coloured particles into a granular host is a brief (<1 s), discrete event, comparable to what occurs in nature following subterranean explosions. The injection assumes a bubble shape while expanding and propagating upwards. In reaction, the upper part of the clastic host moves upward and outward above the ‘bubble’, forming a ‘dome’. The doming effect is much more pronounced for shallow injection depths (thin hosts), with dome angles reaching more than 45°. Significant surface doming is also observed for some full-scale subterranean blasts (e.g. buried nuclear explosions), so it is not an artefact of our setup. What happens next in the experiments depends on the depth of injection and the nature of the host material. With shallow injection into a permeable host (glass beads), the compressed air in the “bubble’ is able to diffuse rapidly through the roof. Meanwhile the coloured beads sediment into the transient cavity, which is also closing laterally because of inward-directed granular flow of the host. Depending on the initial gas pressure in the reservoir, the two-phase flow can “erupt” or not; non-erupting injections produce cylindrical bodies of coloured beads whereas erupting runs produce flaring upward or conical deposits. Changing the particle size of the host glass beads does not have a large effect under the size range investigated (100–200 to 300–400 μm). Doubling the host thickness (injection depth) requires a doubling of the initial gas pressure to produce similar phenomena. Such injections—whether erupting or wholly subterranean—provide a compelling explanation for the origin and characteristics of multiple cross-cutting bodies that have been documented for diatreme and other vent deposits.     

New techniques for the analysis of earthquake sources from local array data with an application to the 1993 Scotts Mills, Oregon, aftershock sequence

We analysed aftershocks recorded by a temporary digital seismic network following the moderate M _w = 5.5 1993, Scotts Mills, Oregon, earthquake. A technique to retrieve source moment tensors from local waveforms was developed, tested, and applied to 41 small earthquakes ( M _w ranging from 1.6 to 3.2). The derived focal mechanisms, although well resolved, are highly variable and do not share a common nodal plane. In contrast, the majority of the events, relocated with a joint hypocentre determination algorithm, collapse to a well-focused plane. The incompatibility of the nodal planes of most events with the plane defined by their locations suggests that the aftershocks did not occur on the fault plane, but tightly around it, outlining the rupture area rather than defining it. Furthermore, the moment tensors reveal stable P -axes, whereas T  -axes plunges are highly dispersed. We detect a rotation of average T  -axis plunge with depth, indicating a change from shallower, predominantly dip-slip mechanisms to deeper strike-slip mechanisms. These characteristics are difficult to explain by remnant stress concentrations on the main-shock rupture plane or asperity- and barrier-type models. We suggest that the aftershocks occurred under the ambient regional stress, triggered by a sudden weakening of the region surrounding the main-shock slip, rather than from a shear stress increase due to the main shock.     

Biodegradation of NOM in Rapid Sand Filters for Removing Iron and Manganese

In order to examine the Corg flow in rapid sand filter columns for the elimination of iron and manganese, reduced groundwater was treated in a pilot plant consisting of a trickling filter column (TF I) followed by a wet type filter column (WF II) and a separate wet type filter column (WF sep). Additionally the effect of filtration on BOM was studied by measuring AOC and BDOC. The biological processes in TF I and WF sep led to an elimination of iron, ammonia, and manganese. Moreover, the filtration decreased the NOM content. 21% and 23% of the TOC were eliminated in TF I and in WF sep, respectively. WF II caused no significant Corg reduction. The calculation of the Corg flow in the filter columns showed that bacteria took part in the TOC elimination. From the TOC removed, about 24% was eliminated by metabolic activities of the bacterial population whereas 86% was adsorbed onto iron sludge. Similar results were obtained for the TF I column and for the WF sep column as well. The calculated Corg flow was confirmed by the BDOC measurements. The filtration process led to a BDOC decrease. TF I and WF sep reduced appoximately 35% of the biodegradable organic carbon. In contrast there was no significant elimination by WF II. The AOC results suggest that an AOC production and an AOC elimination process exist in rapid sand filters for groundwater treatment. In the trickling filter column significant AOC production was found, whereas in the wet type filter columns AOC elimination was predominating.     

Metal extractability in acidic and neutral mine tailings from the Cartagena-La Unión Mining District (SE Spain)

Mine tailings are ubiquitous in the landscapes of mined areas. Metal solubilities were compared in two chemically distinct mine tailings from the old Mining District of Cartagena-La Unión (SE Spain). One of the tailings was acidic (pH 3.0) with 5400 mg/kg Zn, 1900 mg/kg As and 7000 mg/kg Pb. The other was neutral (pH 7.4) with 9100 mg/kg Zn, 5200 mg/kg Pb and 350 mg/kg As. In samples from the acidic tailings, more than 15% of the Zn and 55% of the Cd were extractable with 0.1 M NaNO₃, and distilled water. In the neutral tailings, using the same reagents, less than 1% of the metals were extractable. A sequential extraction procedure revealed that the sum of the residual and the Fe oxide fractions of Cu, Zn and Pb comprised 80–95% in the acidic tailings and 70–90% in the neutral tailings. The acidic mine tailings had a higher metal solubility, resulting in more metal leaching in the short-term, but also a higher fraction of inert metal. In contrast, in the neutral tailings, the metals were evenly distributed between, oxides and the residual fraction. This implies lower metal mobility in the short-term, but that metal mobility may increase in the long-term. When applied to mine tailings, sequential extractions may provide misleading results because the strong cation exchange capacity of some extractants may induce pH changes and thereby significantly change metal solubility.     

The geochemistry of aliphatic and polar organic tracers in sediments from Lake Bera, Malaysia

The molecular distributions of homologous aliphatic lipid compounds (n-alkanes, n-alkanoic acids, n-alkanols, n-alkanals and n-alkan-2-ones) were investigated in sediments of Lake Bera, Malaysia as well as in plant waxes from the vicinity using gas chromatography-mass spectrometry. In addition, triterpenoids of the oleanane, ursane, lupane and friedelane series, and their diagenetic products were also identified. Using the aquatic proxy P_aq, it was found that the n-alkanes present in surface sediments S1, S5 and S6 correspond to an input from emergent macrophytes, whereas in sediments collected from open water (S2, S3 and S4) they correspond to input from submerged/floating macrophytes. The presence of n-alkan-2-ols, a commonly found homologous series in the sediments as well as in the plant wax, is novel here. In addition, the presence of 24-methylcycloart-22-enol and 24-ethylcycloart-22-enol in sediments as well as the plant wax of Pandanus helicopus, a dominant reed around the lake, also supports the input of plant biomarkers to the sediments. The occurrence of 5-membered ring triterpenoid derivatives as major diagenetic products of the triterpenoids identified (e.g. friedelan-2,3-dione) shows that the degradation of the organic matter in the sediments occurs mainly under oxic conditions. Also, the presence of ring-A degraded triterpenoids (dihydroputranjivic acid, 3-nor-2,4-seco-friedelane, 4α- and 4β-3-norfriedelanes, A-norfriedel-10-one, and A-norfriedel-8-en-10-one) and the aromatized triterpenoid hydrocarbons (mono- and triaromatic derivatives) as minor diagenetic products indicates photochemical and microorganism-mediated alteration reactions of natural products in the sediments. Additional novel polyfunctional friedelane derivatives, namely friedelane-2,3-dione, friedelane-1,3-diol-2-one and friedel-1(10)-ene-1,3-diol-2-one were identified for the first time in this study. These novel polyfunctional triterpenoids were inferred to derive from the oxidation of the triterpenoids from higher plants in this oxic tropical environment. For future reference purposes, the mass spectra of the identified polar triterpenoids are also presented here. This study provides important data on the biogeochemistry of organic matter in a tropical lake of SE Asia.     

The climatic signal in varved sediments from Lake C2, northern Ellesmere Island, Canada

Annually-laminated clastic sediments preserve a high resolution proxy record of paleoclimate, provided that allochthonous sedimentation represents a response to meteorological forcing of watershed sediment transfer. Here, we demonstrate this linkage, and illustrate a calibration process using the most recent 40 years of a varve record from Lake C2 (82°50 N; 78°00 W), three years of field measurements, and meteorological data for 1951–92 from nearby AES weather station Alert. Field measurements were used to correlate proxies of the energy available for snowmelt (e.g. air temperature) and daily suspended sediment discharge (SSQ). Our calibration was extended through use of weather data from Alert. Both mean daily air temperature at Echo, and daily SSQ, were well correlated with air temperature at 600 m above Alert, as obtained from the 1200 Z (0800 LST) rawinsonde sounding. Accordingly, we used pooled 1990 and 1992 Alert 600 m data to predict the lagged daily sediment discharge into Lake C2 (adj. r ²=0.43). Daily values were summed each year in order to produce an annual series of predicted sediment transfer to the lake. The original varve chronology was based on eight sediment cores recovered from the deep basin of the lake (>80 m). Although low-frequency fluctuations of the varve and predicted SSQ series agree, slight tuning of the varve record optimizes the correlation between them. Adjustments were based on examination of weather data for specific years, reexamination of sediment core thin sections, and by aligning fluctuations in the two series which closely matched. Although the original chronology is reasonably well correlated with 600 m temperatures at Alert (for JJA mean, r=0.41, significant at 0.01), the adjusted chronology is both better correlated and contains a more precise climate signal (r=0.54 for July mean, significant at 0.01). This is the first calibrated varve record produced from Arctic lake sediments, and demonstrates that varves from Lake C2 contain a paleoclimatic record. We believe the post-facto manipulations required to produce the adjusted varve chronology are reasonable given the uncertainties inherent in varve counting, and the lack of any independent corroborating chronostratigraphic markers.This is the ninth in a series of papers published in this issue on the Taconite Inlet Lakes Project. These papers were collected by Dr R. S. Bradley.     

Climatically induced lake level changes during the last two millennia as reflected in sediments of Laguna Potrok Aike,southern Patagonia (Santa Cruz,Argentina)

The volcanogenic lake Laguna Potrok Aike, Santa Cruz, Argentina, reveals an unprecedented continuous high resolution climatic record for the steppe regions of southern Patagonia. With the applied multi-proxy approach rapid climatic changes before the turn of the first millennium were detected followed by medieval droughts which are intersected by moist and/or cold periods of varying durations and intensities. The total inorganic carbon content was identified as a sensitive lake level indicator. This proxy suggests that during the late Middle Ages (ca. AD 1230–1410) the lake level was rather low representing a signal of the Medieval Climate Anomaly in southeastern Patagonia. At the beginning of the Little Ice Age the lake level rose considerably staying on a high level during the whole period. Subsequently, the lake level lowered again in the course of the 20th century.     

Lipids in selected abyssal benthopelagic animals: links to the epipelagic zone?

A detailed study of the lipids of selected zooplankton species and scavenging amphipods in the near-bottom water layer (15–100 m above bottom, mab) was carried out at the BENGAL site in late summer 1998. Copepoda were the main contributors to the zooplankton, comprising 75% of the total abundance, followed by Ostracoda and Chaetognatha. Calanoid copepods of the family Metridinidae were predominant and accounted for more than 50% of all copepods.Two types of storage lipids were distinguished: triacylglycerols and wax esters. Ostracoda and the polychaete Vanadis sp. stored exclusively triacylglycerols whilst the bulk of the Copepoda accumulated wax esters, with the exception of the family Aetideidae. In the amphipods both lipid classes were found: Eurythenes gryllus stored wax esters and Paralicella spp. and Orchomene sp. triacylglycerols.The fatty acid composition was characterized by a high level of monounsaturated 18:1 (n—9), which is described as characteristic for animals living in the deeper layers of the water column, and to a lesser degree by 16:1 (n—7) and 20:5 (n—3), which are typical components of diatom lipids, and 22:6 (n—3), typical of dinoflagellates. The ratio of 18:1 (n—9):18:1 (n—7) fatty acids was between 5 and 10 in the copepods and indicates a carnivorous/omnivorous feeding behaviour in this group, whereas the higher ratios of 8–18 in the amphipods confirm their necrophagy. The fatty alcohols of the animals storing wax esters were dominated by the monounsaturated isomers 18:1 (n—9) and 18:1 (n—7).The predominance of wax esters as storage lipids in the deep-sea copepods indicates a strong seasonality in the availability of food. This is supported by the high levels of 16:1 (n—7), 20:5 (n—3) and 22:6 (n—3) fatty acids, which point to there being a direct link between the surface primary production and deep-sea copepods, probably via the rapid deposition of phytodetritus.